Quaternary indole derivatives and their manufacture



Patented June 1, 1943 QUATERNARY INDOLE DERIVATIVE AND THEIR MANUFACTURE Curt Engel, Saint Louis, France, and Kurt Pfaehler, Riehen, near Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application April 9, 1940, Serial No. 328,796. In Switzerland May 19, 1937 (C1. Mill-31! 2 Claims.

This application is a continuation-in-part of our application Ser. No. 207,154, filed May 10, 1938.

In the U. S. Patent 2,180,801 there is described a method of converting derivatives of the dihydro indole series into water-soluble bodies by treating with sulphonating agents, under suitable conditions, compounds of the following general structure:

3 which contain in position 2 an aliphatic or alicyclic substituent with more than 5 carbon atoms and which may be substituted in the free positions of the benzene nucleus in any desired manner and in the remaining free positions 1 and 3 by alkyl-, aralkylor aryl-groups. These novel sulphonic acids and their salts are used as Wetting, dispersing, emulsifying and impregnating agents and as detergents, and in particular may be used as lime soap emulsifying agents.

As a result of further study in this field of dihydroindole derivatives it has now been found that new and valuable dihydroindoles are obtained if the water solubility is'produced, not by the introduction of sulphonic acid groups, but by means of quaternary N-atoms.

As in the case of the U. S. Patent 2,180,801, the invention starts from the assumption that in the dihydroindole body of the general structure there is an aliphatic or alicyclic substituent containing more than 5 carbon atoms, in the position 2. The remaining positions can be substituted in the manner set forth in the said Patent 2,180,801.

The novel compounds are made by exhaustively alkylating and/or aralkylating the dihydro-- dyes containing acid groups, so that they are suitable for rendering dyeings fast to water. Finally, it is worth while pointing out that a number of the novel products may also be used as plasticizers, as carbonizing, bactericidal and fungicidal agents.

As in the said Patent 2,180,801 dihydroindoles can quite generally be employed as the raw material for the present process, and these can be readily obtained by known methods, inter alia by splitting 01f water from suitable acylated o-alkylor -aralkyl-s,ubstituted aniline derivatives with sodium alcohola-te (according to Madelung, Ber. d. deutschen chem. Ges. 45, p. 1128), or by means of sodium amide (per Verley, Bull. de la Soc. Chim, vol. 35, pp. 1039- (1924) and vol. 37, pp. l89-91 (1925) and German patent specification No. 479,283) and reducing the indoles thus obtained. Other methods of preparing dihydroindoles and their substitution products may equally well be employed however.

Instead of the catalytic hydrogenation of the indoles, any other known method of producing hydrogenized indoles can, however, be used with equal success.

The following examples illustrate the invention.

Example 1 34 g. of 2-heptadecyl-2:3-dihydroindole, obtained in known manner from Z-heptadecylindole, for example by catalytic hydrogenation with nickel, are dissolved in cos. of chlorobenzene and 17 g. of anhydrous sodium carbonate are added. 20 g. of dimethylsulphate are dropped in at 100 C. and the whole is stirred for 12 hours. Thereupon a further 20 g. of dimethylsulphate are run in drop-wise and the whole is kept a further 6 hours at C Thereafter the soluble portion is filtered off from the undissolved inorganic salts, the chlorobenzene is distilled off by means of steam and the aqueous solution evaporated under a vacuum. A wax-like semisolid mass is obtained which forms a colorless solution in water. The compound corresponds to the formula CH- CnHas (0 Ha) 2 804GB;

By replacing the first quantity of dimethylsulphate by equivalent parts of diethylsulphate or by replacing all the dimethylsulphate by the corresponding ethyl compound, quaternary dihydro- Example 2 34 g. of 2-heptadecyl-2:3-dihydroindole are dissolved in chlorobenzene and anhydrous sodium carbonate added as in Example 1. 20 g. of 'dimethylsulphate are dropped in and the whole stirred for 12 hours. 20 g. of benzylchloride (or also 27 or 30 g. of the bromide of technical stearylor dodecyl alcohol) are then added in drops and heated to 140 C. for 6 hours. After the salts have been filtered off, the chlorobenzene and excess of benzylchloride are removed by steam. The aqueous solution obtained may be etherised and evaporated to the dry state under a vacuum. A final product having similar properties to the product of Example 1 obtained, and aqueous solutions of the product likewise have a high foaming capacity. The formula of the product of the present example is the following:

Example 3 v 34 g. of. 2 heptadecyl-2:3-dihydroindole are dissolved in 100 cos. of chlorobenzene, 1'7 g. of

anhydroussodium carbonate added, 20 g. of dimethylsulphate added in drops at 100 C. and the Whole is stirred for 12 hours. 15 g. of chloracetic ethyl or methyl ester are then added gradually and the mixture heated to 140 C. for 6 hours. After the salts separating out have been filtered off, the .chlorobenzene is distilled off by means of steam and, where required, the aqueous solution cbtainedis etherised and evaporated to dry-- ness under a vacuum. ,-A We: readily solu ble in water, is obtained.

Example 4 34 g. of Z-heptadecyl-Z:3-dihydroindole are, as described in the above example, first treated with 20 g. of dimethylsulphate at 100 C. for 12 hours, and then 12 g. of glycerin a-chlorhydrin is ':-added .drop by drop and the whole heated 6 hours tel-20. C. After the .saltshave been filtered off, the chlorobenzene is distilled OK with steam and, if desired, the aqueous solution is separated from insoluble impurities by filtration. The final product, which is obtained as set forth above,

- parent material ortho-aminoethylbenzene,

mologues of ortho-methyl-aminobenzene.

meta- 0r paraxylidine, mesidine or other ho- Erample 151 g. ofethylene oxide are reacted on 28 g. of 2-undecyl-2:3-dihydroinclole in a closed vessel at 10O120" C. g. of this reaction product are dissolved in 20 cos. of toluene and 17 g. of anhydrous sodium carbonate are added. 20 g. of dimethyl-sulphate are added in drops at C. and the whole stirred for 12 hours. Thereupon, a further 20 g. of dimethylsulphate are added in drops and the Whole is heated at C, for 6 hours. After filtering off the salts of the toluene is removed by steam distillation and the aqueous solution obtained is evaporated to dryness under a vacuum. A semi solid, Waxy mass is obtained.

What we claim is: y

1. The colorless quaternary dihydro-indoles oi the formula the first-named radical constitutes X andthe second-named radical constitutes W; Z represents a member of the group consisting of H and CH3; and n represents one of the integers 1 and 2.

2. The colorless quaternary dihydroindoleqof the following formula CIIzOgGs being a wax-like semi-solid mass forming colorless aqueous solutions of high capillary activity.

CURT ENGEL. KURT P'FAEHLER. 

